1

ORGANOMETALLIC CHEMISTRY
1. Write a mechanism for the conversion of allyl alcohol (CH
2
=CH-CH
2
OH) to propanal
using HCo(CO)
4
as catalyst.
2. The following compounds are known: (C
7
H
7
)Cr(C
5
H
5
), (C
6
H
6
)Mn(C
5
H
5
), (C
5
H
5
)
2
Fe,
(C
4
H
4
)Co(C
5
H
5
). Suppose you wish to make a compound which contained both a
cyclopentadienyl ring and a three-membered ring, show how you might attempt to
synthesise such a compound.
3. Predict reasonable product(s) for the following reactions:
(i) Nb(CH
2
CMe
3
)
4
Cl + 2PMe
3
A + B
(ii) (Me
3
CCH
2
)
3
TaCl
2
+ 2Me
3
CCH
2
Li C
(iii) W(CO)
6
+ LiMe D
(iv) D + Me
3
O
+
E
4. (a) Suggest a plausible mechanism for the following reaction:
RhH(CO)(PPh
3
)
3
+ C
2
H
4
+ PhCOCl ----> PhCOC
2
H
5
+ RhCl(CO)(PPh
3
)
2
+ PPh
3

5. Identify compounds A to D and briefly comment on the reactions.
Na[(
5
-C
5
H
5
)W(CO)
3
]

+ CH
2
= CH - CH
2
Cl


A
NaBH
4
HPF
6
h
D
C B

B: %W = 35.4; %C = 25.4; %P = 5.96
Mass spectrum M
+
(based on
184
W): C = 376; D = 346
[C = 12, P = 31, H = 1, Na = 23, F = 19, B = 11, O = 16, Cl = 35.5]
6. Show how a hydrido species can cause isomerisation of hex-1-ene to cis and trans hex-
2-enes.
7. The complex [RhCl(PPh
3
)
3
] is well-known as a catalyst for the alkene hydrogenation.
Present a catalytic cycle for this process.
Although useful for a wide range of alkenes, the presence of an aldehyde functionality in
the alkene can cause loss of activity. Account for this observation.
This complex has been shown to catalyse an isomerisation of 4-pentenals. The fate of
the majority of the deuterium label in the aldehyde hydrogen site is shown below:
2
O
D
D
O

In the light of the reactions you have discussed above, suggest a catalytic cycle for this
isomerisation.
8. Give a method of synthesis for each of the following compounds, specifying the
chemical(s) used and nature of reaction(s) involved. (Starting material given in
parentheses)
(i) Ferrocene (C
5
H
6
)
(ii) Aminoferrocene (ferrocene)
(iii)
C
CH
3
OCH
3
(CO)
5
W
(W(CO)
6
)
(iv)
CH
2
CH
3
(C
5
H
5
)
2
Ta
[(C
5
H
5
)
2
Ta(CH
3
)
3
]
(v)
O O
H
3
C
H
3
C
Fe(CO)
3
CH
3
CH
3
[Fe(CO)
5
]
(vi)
Br
[Cp
2
ZrHCl]
(vii) (C
5
H
5
)Mn(C
6
H
6
) [(C
5
H
5
)MnCl]
(viii) [(
5
-C
5
H
5
)Fe(CO)
2
(C
2
H
4
)]
+
from [(
5
-C
5
H
5
)Fe(CO)
2
]
2
(ix) [(
5
-C
5
H
5
)Ni(-C
5
H
5
)Ni(
5
-C
5
H
5
)]
+
from NiCl
2